JPH0759699B2 - Water and oil repellent composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water / oil repellent composition.

Conventional technology and its problems In order to impart water and oil repellency to conventional fiber products, a homologous polymer of fluorine-containing methacrylic acid ester or acrylic acid ester, and a monomer copolymerizable with the methacrylic acid ester or acrylic acid ester are used. Fluorine compounds such as the copolymers have been used. However, these fluorine-containing compounds only impart water and oil repellency with low durability, and do not impart another important property required for the fiber treatment agent, that is, antifouling property.

In order to solve the above problems, an antifouling composition containing a fluorine-containing compound (JP-A-54-74000 and JP-A-59-33315).
No.), a water- and oil-repellent composition containing a fluorine-containing urethane compound and a functional group-containing organopolysiloxane (Japanese Patent Application Laid-Open No. Sho 60-90).
−81278) and the like have been proposed. These compositions have the desirable property of imparting durable water and oil repellency and stain resistance to textiles.

However, with the recent demand for higher-grade textile products, it has been desired to develop a water- and oil-repellent agent capable of imparting more excellent water and oil repellency and antifouling property.

Means for Solving the Problems The present inventor has conducted extensive studies in view of the problems of the prior art, and as a result, a silane or siloxane compound having a perfluoroalkyl group was added with an organosilsesquioxane ladder polymer. By blending, a water- and oil-repellent agent capable of imparting remarkably excellent antifouling property and water and oil repellency to a fiber product can be obtained, and the water and oil repellency imparted to the fiber by the water and oil repellent agent can be obtained. The present invention has been completed by finding that oily durability is extremely high.

That is, the present invention relates to a water / oil repellent composition comprising (A) a silane or siloxane compound having a perfluoroalkyl group, and (B) a ladder polymer of an organosilsesquioxane.

Examples of the silane or siloxane compound having a perfluoroalkyl group used in the present invention include compounds represented by the following general formulas (1) to (3), and hydrolyzed condensates thereof.

_{R f XSi (CH 3) k} (Z) 3-k (1) wherein, R _f represents a perfluoroalkyl group having 4 to 20 carbon atoms. X is an acetyleneoxy group having 1 to 4 carbon atoms, 1 carbon atom
To 4 alkylene group, group _{-C 2 H 3 (A) C} l H 2l - ( wherein,
A represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydrogen group or an alkylcarbonyloxy group having 1 to 4 carbon atoms in the alkyl moiety. l shows the integer of 0-4. ) Or a group _{-SO 2 N (B) C m} H 2m - shows a (wherein, B is .m represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is an integer of 0 to 6).. Z represents an alkoxy group having 1 to 4 carbon atoms. k represents 0 or 1. ] _{R f Y (W) (CH} 2) 3 Si (CH 3) k (Z) 3-k (2) wherein, R _f, Z and k are as defined above. Y is a group -C ₂ H
₃ (A) _Cl H _2l- (in the formula, A and l are the same as above). W is a group -S -, - NH -, - NH (CH 2) 2 NH-, Indicates. ] _{R f XOSi (CH 3) k} (Z) 3-k (3) wherein, R _f, X, Z and k are as defined above. Specific examples of the fluorine-containing silane or siloxane compound represented by the above general formulas (1) to (3) will be given below.

R _f CH ₂ CH ₂ Si (OCH ₃ ) ₃ R _f CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ R _f CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ R _f CH ₂ CH ₂ Si ( _{CH 3) (OC 2 H 5} ) 2 R f CH 2 CH 2 Si (OCOCH 3) 3 R f CH 2 CH 2 Si (CH 3) (OCOCH 3) 2 R _f (CH ₂ ) ₂ OSi (OCH ₃ ) ₃ R _f (CH ₂ ) ₂ OSi (CH ₃ ) (OCH ₃ ) ₂ R _f (CH ₂ ) ₂ OSi (OC ₂ H ₅ ) ₃ R _f (CH ₂ ) ₂ OSi (CH ₃ ) (OC ₂ H ₅ ) ₂ R _f (CH ₂ ) ₂ OSi (OCOCH ₃ ) ₃ R _f (CH ₂ ) ₂ OSi (CH ₃ ) (OCOCH ₃ ) ₂ [wherein R _f Represents C _n F _{2n + 1} − (n represents an integer of 4 to 20). The partial hydrolysis-condensation product of the compounds of the above general formulas (1) to (3) is one in which a part of the Z group becomes a silanol group and a dehydration condensation reaction is performed to form a 2 to 20 mer.

The silane or siloxane compounds having a perfluoroalkyl group represented by the above general formulas (1) to (3) or their partial hydrolysis-condensation products used in the present invention are known compounds. 172242, JP-A-58
-172243, JP-A-58-172244, JP-A-58-172245
No. 58,172,246, and British Patent No. 1418465, but the invention is not limited thereto.

The organosilsesquioxane ladder polymer used in the present invention has the general formula [In the formula, R'represents a methyl group, a phenyl group or the like. However,
A portion of the oxygen atoms connecting the two longer siloxane chains may be replaced by two hydroxyl groups. ] It is an addition polymer of a hypothetical monomer R'SiO _1.5 (organosilsesquioxane) having a ladder-shaped regular skeleton structure represented by the following formula. Usually, one or more selected from trifunctional organosilanes such as methyltrichlorosilane, phenyltrichlorosilane, methyltriethoxysilane, and phenyltriethoxysilane are hydrolyzed to obtain the resulting hydrolysis product. It is produced by polycondensation of the product to equilibrate or further polycondensation.

When the ladder polymer of organosilsesquioxane is strictly defined, the general formula is [In formula, R is the same substituent, a hydrogen atom, C1-C1
6 represents an alkyl group, a cyclohexyl group, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group. n'represents an integer of 2 to 6. ] It is a polymer in which one kind or two or more kinds selected from the group consisting of the oligomer of organosilsesquioxane represented by the above is bonded in a chain or ring. The degree of polymerization of this ladder polymer is Is about 2 to 200, and 10% or less of oxygen atoms connecting two longer siloxane chains may be substituted with two hydroxyl groups. When the ladder polymer is a chain polymer, a halogen atom such as Cl, an alkoxy group having 1 to 6 carbon atoms, an acetoxy group or a hydroxyl group is bonded to the Si terminal, and the Si terminal is bonded to the Si terminal. Correspondingly, an oxygen atom is replaced by a halogen atom, or an alkyl group having 1 to 6 carbon atoms, an acetyl group or a hydrogen atom is bonded to the oxygen atom.

The organosilsesquioxane ladder polymer is a known compound, and is known as Encyclopedia of Polymer Science and Technology (Encyclopedia
of Polymer Science and Technology Vol.12 pp.
500-501 1970), Japanese Patent Publication No. 40-15989, Japanese Patent Laid-Open No. 56-582.
It can be manufactured by the method described in No. 6 etc., but it goes without saying that the materials used in the present invention are not limited to those manufactured by the method listed here.

Specific examples of the organosilsesquioxane are shown below.

[In the formula, the ratio of the methyl group and the phenyl group is 2: 1,
Each group is not necessarily in this position. ] [In the formula, the ratio of the methyl group and the phenyl group is 1: 4,
Each group is not necessarily in this position. ] The above compounds I, II, III, IV and V are trade names GR10, respectively.
0, GR150, GR650, GR908 and GR950 (manufactured by Owens-Illinois, USA).

In the present invention, the compounding ratio of the silane or siloxane compound having a perfluoroalkyl group and the ladder polymer of organosilsesquioxane is usually 99.9 by weight:
You can select from a wide range of 0.1 to 0.1: 99.9,
In order not to impair the water / oil repellency and antifouling performance of the composition, it is preferably about 30:70 to 99.9: 0.1.

In treating a textile product using the water / oil repellent of the present invention, any ordinary method can be adopted. For example, the water / oil repellent of the present invention is dissolved or dispersed in an organic solvent or an aqueous medium,
Then, the obtained solution or dispersion may be applied to the inner surface of the mold by operations such as spraying the fiber product, brushing the fiber product, and immersing the fiber product in the solution or dispersion. As the organic solvent used, for example, benzene, toluene, aromatic hydrocarbons such as xylene, methanol,
Ethanol, butanol, propanol, isopropanol and other alcohols, acetone, methyl ethyl ketone and other ketones, ethyl acetate, ethyl acetate and other esters, dioxane, tetrahydrofuran, cellosolve and other ethers, methyl chloroform, tetrachlorodifluoroethane, 1 Examples thereof include halogenated hydrocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, trichloroethylene and tetrachloroethylene, nitriles such as acetonitrile, dimethylformamide and metaxylenehexafluoride. These organic solvents can be used alone or in combination. When an organic solvent solution or an aqueous dispersion of the water / oil repellent of the present invention is produced, the concentration of the water / oil repellent is usually about 0.01 to 40% by weight, preferably
It may be about 0.07 to 3% by weight. If a propellant such as dichlorofluoromethane, monofluorotrichloroethane or dichlorotetrafluoroethane is added to the solution or dispersion of the water / oil repellent of the present invention to form an aerosol, the treatment of textile products can be simplified by spraying. it can.

In the present invention, by condensing the silane or siloxane compound having a perfluoroalkyl group which is the component (A) of the composition of the present invention and the ladder polymer of organosilsesquioxane which is the component (B), The water / oil repellency and antifouling property of the composition of the present invention can be further improved. In the condensation reaction, for example, i) the water / oil repellent of the present invention is heated in the above solvent or an aqueous medium at about 50 to 200 ° C. to precondensate the fluorine-containing compound and the organosilsesquioxane ladder polymer. Ii) After applying a water / oil repellent to a textile product, heat treatment is performed at about 40 to 400 ° C., iii) A catalyst may be added. Further, in the cases of i) and ii), a catalyst may be added to accelerate the condensation reaction. Specific examples of the catalyst include, for example, pyridine, amine-containing silicone, amines such as triethanolamine, tetramethylammonium hydroxide, melamine formaldehyde, bases such as benzyltrimethylammonium hydroxide, phenylphosphonic acid, citric acid, formic acid, hydrochloric acid, Examples thereof include metal salts of inorganic acids or organic acids such as acetic acid, nitric acid, sulfuric acid and phosphoric acid. Examples of the metal of the metal salt include tin, copper, iron, zinc, sodium, potassium, aluminum and the like. Although the amount of the catalyst added is not particularly limited, it is usually about 0.01 to 6% by weight of the water / oil repellent of the present invention.

If desired, various additives such as antistatic agents, softening agents, slip agents, insect repellents, flame retardants, occupancy and occupation stabilizers may be added to the water and oil repellent agent of the present invention.

The water and oil repellent of the present invention can be used for any ordinary textiles.

EFFECTS OF THE INVENTION The water and oil repellent of the present invention can impart remarkably excellent antifouling property and extremely high water and oil repellency to virtually all textiles.

EXAMPLES The present invention will be further clarified with reference to synthesis examples, examples and comparative examples of silane or siloxane compounds.
In the following, when simply referred to as “parts” or “%”, it means “parts by weight” or “% by weight”, respectively.

Synthesis Example 1 CF ₃ CF ₂ (CF ₂ CF ₂ ) _x CH = CH ₂ (where x is 3, 4, 5, 6 or 7
It is a mixture of The average value of x is 3.6. Hereinafter referred to as compound A. ) 75.9 g (0.150 mol), HSiCl ₃ 24.5 g (0.185 mol)
Mol), 0.036 g (0.00007 mol) of H ₂ PtCl ₆ and 0.45 ml of dry isopropyl alcohol were charged into a 100 ml stainless autoclave and reacted at 85 ° C. for 6 hours.

After completion of the reaction, distill by distillation at 120 ℃ -127 ℃ / 25mmHg
74.9 g of the reaction product of the distillate was obtained. When the reaction product was analyzed by gas chromatography, IR, and NMR, it was CF ₃ CF ₂ (CF ₂ CF ₂ ) _x CH ₂ CH ₂ SiCl ₃ (x is the same as above; hereinafter referred to as compound B). The conversion rate of the compound A was 98%.

200 g of compound B21 g and trichlorotrifluoroethane 30 g
Place in a ml eggplant-shaped flask and add 40 g of triethylamine (0.4
Mol) and 30 g (0.9 mol) of methanol, and add 1 at 50 ° C.
Reacted for hours.

After completion of the reaction, triethylamine, methanol and trichlorotrifluoroethane were completely distilled off, trichlorotrifluoroethane was added again, and triethylamine hydrochloride was passed through a Kiriyama funnel. Trichlorotrifluoroethane of the obtained liquid was distilled off to obtain a reaction product. From the gas chromatograph, IR, and NMR, it was confirmed that the reaction product was CF ₃ CF ₂ (CF ₂ CF ₂ ) _x CH ₂ CH ₂ Si (OCH ₃ ) ₃ (x is the same as above. . The yield was 100%.

Synthesis example 2 (X is a mixture of 3, 4, 5, 6 or 7 x
The average value of is 3.6. Hereinafter referred to as compound C. ) 19.8g (0.037
5 mol H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ 8.3 g (0.037 mol)
The mixture was placed in a 0 ml eggplant-shaped flask and reacted at 60 ° C. for 12 hours. After the reaction was completed, the reaction product was analyzed by NMR and IR. Was identified as (W 'is -NHCH ₂ shows a CH ₂ NH-.) (Hereinafter referred to as compound). The conversion rate of the compound C was 95%.

Synthesis Example 3 In Synthesis Example 1, the amount of Compound A used was changed to 94.0 g (0.181 mol) and HSiCl ₃ was changed to 24.5 g (0.185 mol).
Except that 25.0 g (0.217 mol) of HSi (CH ₃ ) Cl ₂ is used,
Perform the same operation as in Synthesis Example 1, Got The conversion rate of the compound A was 98%. Then, the same operation as in Synthesis Example 1 is performed, (Hereinafter referred to as compound) was obtained with a yield of 100%.

Synthesis Example 4 The compound (x is 3, 4, 5, 6, 7 obtained in Synthesis Example 1
It is a mixture of The average value of x is 3.6. ) 9.65g (0.
0167 mol) and ion-exchanged water 0.60 g (0.0334 mol) 50 m
It was charged in a l-shaped eggplant-shaped flask and reacted at 80 ° C. for 1 hour. After completion of the reaction, 1 mol of a methoxy group and 1 mol of a methyl group were desorbed from 1 mol of a silicon atom by NMR and elemental analysis. [In the formula, X is the same as above. a is a mixture of 3 to 20. ] It was confirmed that it was a partially hydrolyzed condensate (hereinafter referred to as a compound). In addition, the Si side end is CH ₃ O-
Alternatively, HO- is bound or is bound to the O-side end to form a ring, and the O-side end is bound to CH ₃ -or H- or is bound to the Si-side end to form a ring. Conceivable.

Example 1 1 Purpose The water and oil repellents of the present invention and conventional water and oil repellents were subjected to water repellency, oil repellency, dry soil resistance and washing resistance tests, and their performances were measured.

2 Water and oil repellent used (A) Water and oil repellent of the present invention Four kinds of fluorine-containing silane or siloxane compounds obtained in Synthesis Examples 1 to 4 and two kinds of ladder organosiloxanes (hereinafter PLOS and 9) and 9 types of water and oil repellents of the present invention were produced at the blending ratios shown in Table 1.

[In the formula, the ratio of the methyl group and the phenyl group is 2: 1,
Each group is not necessarily in this position. Also, 3 mol% of the oxygen atoms connecting two longer siloxane chains are 2
It is substituted with hydroxyl groups. ] In the solvent column in Table 1, IPA is isopropyl alcohol and S-3 is 1,1,2-trifluorotrichloroethane (the same applies hereinafter).

(C) Water- and oil-repellent agent of Production Method Nos. 1 to 9 A fluorine-containing compound, PLOS and a solvent (and an additive) are placed in a four-necked flask equipped with a cooler and stirred and mixed at room temperature for 10 minutes to give a water- and oil-repellent agent Obtained. A catalyst was added to Nos. 8 and 9 as shown in Table 1 to condense the fluorine-containing compound and PLOS.

(B) Conventional Water / Oil Repellent Table 2 shows the conventional water / oil repellent used as a comparative example.

3 Performance Test The water and oil repellents of the present invention Nos. 1 to 9 (Examples 1 to 1) obtained above.
9) and conventional water and oil repellent Nos. 10 to 15 (Comparative Examples 10 to 15)
The tetron tropical cloth and the nylon taffeta cloth treated with were subjected to water and oil repellency, dry sole resistance and washing resistance tests. The results are shown in Table 6. The treatment and each test were conducted as follows.

1) Treatment For the treatment, the water / oil repellent composition of the water / oil repellent composition shown in Table 1 was adjusted to a concentration of 0.4% in the solvent of the solvent composition shown in Table 1, and the solution (30 × (30 cm) is dipped, squeezed with a mangle (squeezing rate 50%), and dried at room temperature for 2 hours.
In addition, the component amounts of the additives in Table 1 are indicated with the above solution being 100% by weight.

2) Water and oil repellency test Water repellency is represented by the water repellency No. by the spray method of JIS L-1092 (see Table 3 below), and the oil repellency is shown in Table 4 below. Above, a few drops in two places (diameter about 4m
m) for 30 seconds and then determine the permeation state (AATCC TM
118-1966).

3) Dry sole resistance test Dry sole resistance is determined by cutting the sample cloth into 5 x 7 cm, putting the dry stain (twice the weight of the sample) and the sample in the container shown in Table 5 below for 3 minutes. Mix and stir to contaminate. After the contamination, the excess stain was removed with an electric vacuum cleaner, and the reflectance was measured to obtain and evaluate the degree of contamination. The pollution degree is calculated by the following formula.

Pollution degree (%) = (RO-R / RO) x 100 RO: reflectance of uncontaminated cloth R: reflectance of contaminated cloth 4) Washing resistance test Washing resistance is measured using a household electric washing machine with a commercial detergent "Zab" (Zab enzyme) 2g /, bath ratio 1:30, 5 minutes at 40 ° C →
Centrifugal dehydration → washing with water for 2 minutes → centrifugal dehydration → washing with water for 2 minutes → centrifugal dehydration as one washing cycle, washing 5 times and 20 times, followed by hot air drying at 80 ° C. for 3 minutes, and measurement of water and oil repellency ( Home laundry JIS.L.0217-76 103).

From Table 6, it can be seen that the water / oil repellent of the present invention can impart excellent antifouling property and extremely high water / oil repellency to textiles as compared with the conventional water / oil repellent.

Claims (2)

[Claims] 1. A water and oil repellent composition comprising (A) a silane or siloxane compound having a perfluoroalkyl group and (B) a ladder polymer of an organosilsesquioxane. 2. A ladder polymer of (A) 30 to 99.9% by weight of a silane or siloxane compound having a perfluoroalkyl group and (B) an organosilsesquioxane ladder polymer.
The water / oil repellent composition according to claim 1, which comprises ˜70% by weight.